Effect of the interfacial potential distribution on the measurement of the rate constant for electron transfer between electrodes and redox adsorbates

Langmuir

Volumn 14, Issue 21, 1998, Pages 6291-6296

  Honeychurch, Michael J ^a,b  

^a UNIVERSITY OF HAWAII   (United States)

^b UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

COMPUTER SIMULATION; CYCLIC VOLTAMMETRY; ELECTRIC POTENTIAL; ELECTRON TRANSPORT PROPERTIES; INTERFACES (MATERIALS); MATHEMATICAL MODELS; RATE CONSTANTS; REDOX REACTIONS;

DOUBLE-LAYER EFFECTS; INTERFACIAL POTENTIAL DISTRIBUTION; REDOX ADSORBATES;

CHARGE TRANSFER;

EID: 0032182733     PISSN: 07437463     EISSN: None     Source Type: Journal    
DOI: 10.1021/la980150b     Document Type: Article

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19. The equations for both the anodic and cathodic currents have been given separately to highlight that the reversible peak potentials for the cathodic and anodic reactions need not be the same, and therefore the overpotentials need not be the same for sweeps in both directions. In other words, the anodic and cathodic currents are not necessarily mirrors of each other.
20. Strictly speaking the definition of m should include the sign on v. However, by the definition of ψ given in eq 6, the dimensionless current must have the same sign for both the anodic and cathodic sweeps. Taking only the magnitude of v allows the sign of ψ to be the same as the current in both directions. This also allows m to always be positive.
21. p< 200 mV the working curve constructed from Table 1 in ref 13.
22. According to Wolfram Research the Mathamatica notebooks are cross platform, so while these calculations were performed on a Power Macintosh computer the notebooks should be able to be used on other platforms without modification or conversion.
23. Wolfram, S. The Mathematica Book, Trans. 3rd ed.; Cambridge University Press/Wolfram Media: New York/Champaign, 1996; p 1403.
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